U.S. patent number 3,856,540 [Application Number 05/327,556] was granted by the patent office on 1974-12-24 for cement additive.
This patent grant is currently assigned to Denki Kagaku Kogyo Kabushiki Kaisha. Invention is credited to Tsutomu Mizunuma, Takeo Yoshida.
United States Patent |
3,856,540 |
Mizunuma , et al. |
December 24, 1974 |
CEMENT ADDITIVE
Abstract
A cement additive consisting of calcium sulfate and calcium
fluoroaluminate having the chemical formula 3CaO.sup.. 3Al.sub.2
O.sub.3.sup.. CaF.sub.2.
Inventors: |
Mizunuma; Tsutomu (Ohmi,
JA), Yoshida; Takeo (Ohmi, JA) |
Assignee: |
Denki Kagaku Kogyo Kabushiki
Kaisha (Tokyo, JA)
|
Family
ID: |
11746713 |
Appl.
No.: |
05/327,556 |
Filed: |
January 26, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Jan 28, 1972 [JA] |
|
|
47-10312 |
|
Current U.S.
Class: |
106/705; 106/734;
106/735 |
Current CPC
Class: |
C04B
22/0093 (20130101); C04B 28/02 (20130101); C04B
22/00 (20130101); C04B 22/14 (20130101); C04B
28/02 (20130101) |
Current International
Class: |
C04B
22/00 (20060101); C04B 28/00 (20060101); C04B
28/02 (20060101); C04b 007/02 () |
Field of
Search: |
;106/89,314,315 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Sheehan; John P.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A cement additive comprising calcium sulfate from 20 to 90% by
weight and calcium fluoroaluminate having the chemical formula
3CaO.sup.. 3Al.sub.2 O.sub.3.sup.. CaF.sub.2 from 80 to 10% by
weight.
2. A cement composition comprising cement from 99 to 70% by weight
and a cement additive from 1 to 30% by weight, said cement additive
comprising calcium sulfate from 20 to 90% by weight and calcium
fluoroaluminate having the chemical formula 3CaO.sup.. 3Al.sub.2
O.sub.3.sup.. CaF.sub.2 from 80 to 10% by weight.
Description
This invention relates to a cement additive and particularly to a
cement additive providing both properties of expansion and strength
to a cement by admixing the cement additive to the cement.
Conventional Portland cement has proper ultimate strength and is
generally used in the field for setting engineering machines,
constructions and molded concrete products, but has a relatively
slower hardening property and a lower strength at the early stage
of hardening than the other cements, for example aluminous cement.
Therefore the application of this cement is limited. Furthermore,
conventional Portland cement has a fault that said cement shrinks
during the hardening and therefore cracks are formed in concrete
constructions.
The progress of the industrial technic in the recent year demands
rapid finishing in various workings.
Various proposals have been made with respect to cement expanding
agents composed of calcium, alumina and gypsum. For example, an
expanding cement composed of alumina cement, gypsum and Portland
cement still possesses an insufficient expansion rate. Further, a
cement expanding agent consisting mainly of a calcium
sulfoaluminate series compound is superior to the above expanding
system with respect to its expansion properties. However, since
free CaO contained in the calcium sulfoaluminate series expanding
agent has a very low resistance to moisture, the expanding agent is
weathered and thus the expansivity of the agent decreases
considerably.
A cement expanding agent consisting mainly of gypsum possesses
strength deficiencies, involves a long aging period, and is still
insufficient in the practical use.
The inventors have made investigations in order to obviate these
drawbacks and accomplished the present invention.
It is an object of this invention to provide a cement additive
which will allow molds to be used three to four times per day
instead of once a day in the field of producing molded concrete
products.
It is a further object of the present invention to provide a cement
additive permitting the rapid working for setting engineering
machines and constructions.
Another object of the invention is to provide a cement additive
preventing in mortar and concrete which are caused by shrinkage of
cement in the hardening and drying.
The present invention consists in a cement additive consisting
mainly of a mixture of calcium sulfate and calcium fluoroaluminate
having the chemical formula 3CaO.sup.. 3Al.sub.2 O.sub.3.sup..
CaF.sub.2. The calcium fluoroaluminate is produced by mixing lime,
bauxite and fluorspar in such an amount that the mineral of the
resulting product becomes 3CaO.sup.. 3Al.sub.2 O.sub.3.sup..
CaF.sub.2 and burning the resulting mixture at a temperature of
1,200.degree.-1,400.degree. C.
If the temperature is lower or higher than the above range and the
cooling rate of the resulting clinker is not proper, side reactions
occur and therefore the desired results are not obtained.
The above ternary compound 3CaO.sup.. 3Al.sub.2 O.sub.3.sup..
CaF.sub.2 is per se known in the art and has been described by J.
K. Leary [Nature, 194(482) (1962)79].
The mixing ratio of the above described calcium fluoroaluminate and
calcium sulfate is 80-10% by weight of calcium fluoroaluminate and
20-90% by weight of calcium sulfate.
When the resulting mixture is combined with conventional Portland
cement in an amount of 1-30% by weight, the set time of the cement
may be shortened in a controllable way and the cement will develop
a high strength upon setting, and simultaneously the cement
composition will develop an effective expansion.
The cements to be used in the present invention include Portland
blast furnace cement, fly ash cement and silica cement other than
conventional Portland cement.
Furthermore, the cement additive may be used together with a
dispersing agent, AE agent, water proofing agent, and the like.
Calcium sulfate in accordance with this invention may be used in
the form of dihydrate, hemihydrate and anhydrate.
Since the content of free CaO in the cement additive according to
the present invention is very low, the deterioration of properties
due to weathering hardly occurs, and the additive is stable.
Accordingly, the expansion rate of the cement additive is
considerably higher than those of the above described cement
expanding agents composed of alumina cement and gypsum or of
12CaO.sup.. 7Al.sub.2 O.sub.3 and gypsum. Another merit of the
present invention is that the expansion rate of the cement additive
can be regulated by varying the mixing ratio of 3CaO.sup..
3Al.sub.2 O.sub.3.sup.. CaF.sub.2 and calcium sulfate. Moreover,
when the cement additive having a high content of 3CaO.sup..
3Al.sub.2 O.sub.3.sup.. CaF.sub.2 and a low content of calcium
sulfate is mixed with Portland cement, the strength of the Portland
cement can be increased considerably. Accordingly, the cement
additive of the present invention can be also used as a
strength-improving agent of cement. Moreover, when a mixing ratio
of the cement additive to cement is increased or the particle size
of the cement additive is decreased, a desired strength can be
obtained in a short time. Accordingly, the cement additive can be
also used as a quick hardening additive. In this case, when calcium
hydroxide or sodium carbonate is added to the cement additive as a
third component, the rapid hardening time can be more
accelerated.
For a better understanding of the present invention, reference is
taken to the accompanying drawing, wherein:
The single FIGURE is an X-ray diffraction diagram of the 3CaO.sup..
3Al.sub.2 O.sub.3.sup.. CaF.sub.2 clinker according to the present
invention.
The following examples are given for the purpose of illustration of
this invention and are not intended as limitations thereof.
EXAMPLE 1
Commercially available calcium carbonate, commercially available
alumina and fluorspar were mixed in the following proportions.
______________________________________ % by weight
______________________________________ Calcium carbonate (purity
99.0%) 43.8 Alumina (purity 99.5%) 44.3 Fluorspar (purity 95.0%)
11.9 100.0 ______________________________________
The resulting mixture was charged into a platinum crucible and
burned at 1,350.degree. C for 2 hours in an electric furnace. The
resulting clinker was confirmed from the X-ray analysis curve as
shown in the FIGURE that the clinker had a composition of
3CaO.sup.. 3Al.sub.2 O.sub.3.sup.. CaF.sub.2. Chemically analytical
value according to JIS R5202 is shown in the following Table 1.
Table 1
__________________________________________________________________________
Ig-loss SiO.sub.2 Fe.sub.2 O.sub.3 Al.sub.2 O.sub.3 CaO TiO.sub.2
MgO CaF.sub.2 Total F-CaO
__________________________________________________________________________
0.8% 7.4% 3.8% 45.8% 30.4% 0.5% 0.4% 10.9% 99.8% 0.4%
__________________________________________________________________________
The obtained clinker contained 0.4% by weight of free CaO. The
clinker was mixed with anhydrous calcium sulfate, which was
obtained by burning calcium sulfate dihydrate at 1,000.degree. C
for 1 hour, and the resulting mixture was ground to a specific
surface area of 2,930 cm.sup.2 /g to obtain a cement additive. In
the above mixing, 25% by weight of the clinker (3CaO.sup..
3Al.sub.2 O.sub.3.sup.. CaF.sub.2) and 75% by weight of anhydrous
calcium sulfate were mixed.
The obtained cement additive and conventional Portland cement were
mixed in a weight ratio of 11% : 89% to prepare an enriched cement,
and the expansion rate of enriched cement was measured according to
JIS A1125. The measuring method is as follows. The enriched cement
and sand were mixed in a weight ratio of 1 : 2 to prepare a mortar,
and the mortar was mixed at a water/cement ratio of 65%, formed in
a metal mold having a dimension of 4 .times. 4 .times. 16 cm, cured
for one day in a himid air and taken out from the metal mold. The
length of the mortar sample was used as a base length. The mortar
sample was further cured in water at 20.degree.C for the
predetermined period of time as shown in the following Table 2, and
the length of the sample was compared with the original length,
whereby the expansion rate of the sample was measured. The obtained
result is shown in Table 2.
For comparison, the above experiment was repeated, except that
12CaO.sup.. 7Al.sub.2 O.sub.3 clinker and CaO.sup.. Al.sub.2
O.sub.3 clinker were used instead of the 3CaO.sup.. 3Al.sub.2
O.sub.3.sup.. CaF.sub.2 clinker of the present invention. The
obtained results are also shown in Table 2.
Table 2
__________________________________________________________________________
Present invention Conventional additive 3CaO.3Al.sub.2
O.sub.3.CaF.sub.2 :CaSO.sub.4 12CaO.7Al.sub.2 O.sub.3 : CaSO.sub.4
CaO.Al.sub.2 O.sub.3 :CaSO.sub.4 Mixing ratio 25 : 75 25 : 75 25 :
75 (% by weight)
__________________________________________________________________________
1 day 0.053 0.034 0.012 3 days 0.129 0.025 0.007 Expansion 7 days
0.247 0.022 0.013 rate (%) 14 days 0.295 0.029 0.019 28 days 0.315
0.031 0.021
__________________________________________________________________________
EXAMPLE 2
A cement additive was produced from the 3CaO.sup.. 3Al.sub.2
O.sub.3.sup.. CaF.sub.2 clinker obtained in Example 1 and anhydrous
calcium sulfate in the same manner as described in Example 1,
except that 33% by weight of the clinker and 67% by weight of the
calcium sulfate were mixed and the mixture was ground to a specific
surface area of 5,200 cm.sup.2 /g. The cement additive and
conventional Portland cement were mixed in a weight ratio of 7%:93%
to prepare a mortar. The result of the strength test of the mortar
according to JIS R5201 is shown in the following Table 3 together
with the result in the case of mortar of conventional Portland
cement alone.
Table 3 ______________________________________ Bending strength
Compressive strength (Kg/cm.sup.2) (Kg/cm.sup.2) 3 7 28 3 7 28 days
days days days days days ______________________________________
Conventional Portland 30.3 49.5 79.3 121 229 385 cement Present
36.7 65.7 85.6 172 295 402 invention
______________________________________
EXAMPLE 3
A cement additive was produced from the 3CaO.sup.. 3Al.sub.2
O.sub.3.sup.. CaF.sub.2 clinker obtained in Example 1 and anhydrous
calcium sulfate in the same manner as described in Example 1,
except that 67% by weight of the clinker and 33% by weight of the
calcium sulfate were mixed and the mixture was ground to a specific
surface area of 5,200 cm.sup.2 /g. The cement additive and
conventional Portland cement were mixed in a weight ratio of
30%:70% to prepare an enriched cement. A mortar was prepared in the
following compounding proportions.
______________________________________ Enriched cement 520 g Sand
(Toyoura sand) 1,040 g Water 234 cc
______________________________________
The compressive strength of the formed mortar after curing one hour
was about 50 Kg/cm.sup.2 and that after curing 1 day was 190
Kg/cm.sup.2.
As seen from the above Examples, when the cement additive of the
present invention, which is composed of calcium fluoroaluminate
represented by the chemical formula 3CaO.sup.. 3Al.sub.2
O.sub.3.sup.. CaF.sub.2 and calcium sulfate, is mixed with cement,
the expansion rate of the resulting cement composition is about 10
times or more as compared with the case when conventional cement
additive is used, and moreover the strength of the cement
composition can be increased by about 30% or more. These effects
have never been attained by conventional cement additives.
Therefore, the present invention is very useful for industry.
* * * * *